Enhancement of the Intermolecular Magnetic Exchange through Halogen···Halogen interactions in Bisadeninium Rhenium(IV) Salts

Donatella Armentano, Miguel A. Barquero, Carlos Rojas-dotti, Nicolas Moliner, Giovanni De Munno, Euan K. Brechin, José Martínez-lillo

Research output: Contribution to journalArticlepeer-review

Abstract

Two novel ReIV salts of general formula [H2ade]2[ReIVX6]X2·4H2O [H2ade2+ = 9H-adenine-1,7-diium; X = Cl(1) and Br(2)] have been synthesized and magneto-structurally characterized. 1 and 2 are isostructural salts that crystallize in the orthorhombic system with space group Fdd2. Both compounds are made up of discrete mononuclear [ReIVX6]2- and X- anions and doubly protonated adenine cations. The six-coordinate rhenium(IV) ion is bonded to six halide ligands [X = Cl (1) and Br (2)] in an octahedral geometry. Short intermolecular ReIV−X···X−ReIV interactions, as well as ReIV−X···H−N(H2ade) and ReIV−X···H−Ow hydrogen bonds, are present in the crystal lattice of 1 and 2. Magnetic suscep-tibility measurements on polycrystalline samples of 1 and 2 in the temperature range 2.0-300 K show the occurrence of significant intermolecular antiferromagnetic interactions in both compounds, resulting in the observation of maxima in χM at ca. 6.0 (1) and 12.0 K (2). The larger spin delocalization from the ReIV ion onto their peripheral bromide ligands when compared to the chloride ligands accounts for the enhancement of the magnetic exchange observed in
Original languageEnglish
JournalCrystal Growth and Design
Early online date12 Sep 2017
DOIs
Publication statusE-pub ahead of print - 12 Sep 2017

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